Sulphonated mineral oils rich in sulphur content



Patented Sept. 5, 1939 UNITED :s'rA'rss PATaNroi-"Fics- SULPHONA'I'ED MINERAL OILS RICH IN SUI PHUB. CONTENT Erich Arnold Wcrnickc, signor to The Ichthy corporation of New Jerse Hamburg, 01 00., Y

V Ra lway, N. 1., a

- No Drawing. Original application 1934, Serial No. Dlication In Germany January 11,

organically combined native sulphur, and this division relates obtained by such processes.

Sulphonation products from mineral oils, tar

oils, etc. have the like, known under various proprietary names as Ichthyol, etc. The prodnets of this kind, obtained from oils, have a special importance in Such sulphonation prior art are of a very dark color and opaque, even in thin layers, because, in-their production, the

poses and the strong odor is disagreeable. The presence of such side products necessarily .also masks the efiects of ultimate products in varying degree.

It is an object of the instant invention to produce water-soluble sulphonation products which shall be, free from such objectionable properties which will be of light color, substantially transparent, and of rather pleasant odor or practically odorless, and yet to retain the native combined sulphur substantially unimpaired.

A noteworthy diflerence over the oil-refinement processes hitherto employed lies in the materials which are treated according to processes and objectives disclosed herein and in the parent application, cannot strictly be considered as hydrocarbon oils at all in view of their high sulphur content.. For instance, a total sulphur content of in such oils corresponds to a con- 705,918. Allmt13, 1937, Serial No. 158,915.

sulphur, acid which ,for the purposes of a manner that the the fact that 9, Divided and this antent of organically combined sulphur-compounds of approximately 50-60%, so that the refining exwith may still be i'airly classified as hydrocarbons, cannot simply be applied to the in. l

sulphur oils involved here It must .also be emphasized that usually the original color of the oils in question is not controlling; Thus, a naturally light-colored oil may,

sulphonation procedure several of the indicated processes ,may obviously be combined with each other.

The preliminary separation resinifiable materials, from the body of theoil possibleand, on the other hand,'that no material degree of'sulphonation of sulphur compounds or their removal will take place in the initial stages. When the properties of a given crude sulphuroil or distillate are unfamiliar, the appropriate strength of acid may be empirically ascertained by beginning with relatively low concentrations and progressively increasing the strength in sucoils having less than 2% ofv This separation can. also be carried out with other agents which may be used either alone or combined, thus, for instance, with potash lye, aluminum chloride, phosphoric acid, fullers earth, bleaching clay, and the like, the chemical character of the oil.

That part of the oil, resulting from preceding sulphonations which cannot further be sulphonated may serve as a suitable diluent, in the ultimate carefully controlled sulphonation steps.

Depending upon the thoroughness with which the 'resinifiable material has been removed, and depending further upon the degree of care'observed in the. gradual and controlled sulphonaafter neutralizingthe sulphonation mixture and separating the undissolved portions of the oil, the "applicant has been able to obtain a transparent, clear, water-soluble product of lightyellow to brown color, which impart its color to other substances when mixed with them, whereas without this treatment much darker, non-transparent products, usually having a strong, unpleasant odor, are obtained.

The new products of the,instant process are obtained more or less completely free from the strong unpleasant odors which are so characteristic of the products of the old art, such as bitumen sulphonatum N. F. V.

Following the first careful sulphonation, this can be repeated several times with sulfuric acid of graduated increase in strength, so that each sulphonation process can be regarded as a pretreatment in the sense of the instant application for the sulphonation with the next-following stronger. acid. The acid concentration to be employed in the successive sulphonation steps is downwardly limited by the used in the preceding, step; and by observingthe necessary care in other respects, the concentrations maybe increased up to the stage of fuming sulfuric acid. The greater the difierence in concentration between two successive sulphonation steps, the higher is the sulphonation yield of the second step, but the more care and control will be re red for the production of a sulphonation product of the desired physical and chemical attributes.

The following points broadly characterize the outstanding features of the present invention and its scope: V

(1) Selection of oil high in native organicallycombined sulphur content;

(2) Treatment to remove color-producing and other unwanted substances while nevertheless retaining major part of sulphur compounds before sulphonation;

(3) Reacting the oil containing the sulphur compounds with sulfuric acid to produce sulfonic acids containing not only the major part of the sulphur originally present, but also sulphur introduced by thesulfonating acid and obtaining said sulfonic acids as the desired product in a form free from objectionable color and odor. In both treatments the native sulphur compounds are retained; in the first they are not substantially affected and in the second treatment they are substantially converted into sulfonic acids, which latter serve in a sense as an intermediate for the production of the neutralized solution of the next step;

(4) This complex of clear, light-colored sulfonic acids of the preceding step, is then neutralized, preferably with ammonia, and produces then a clear aqueous solution, with all of the native sulphur substantially retained.

depending on does not materially -60 cc. sulphuric acid of 90% acid concentration .monium sulphate and 9.57%

The end product obtained according to the present invention may be transformed to the desired consistency by adding water or by evaporation. The removal of excessive amounts of sulfates as may be desired, can be carried out in any well known manner, either after the neutralization, for instance by extraction with solvents.

" According to this invention sulphur-bearing petroleum or other oils, for instance from Italian mineral coal, Middle-German brown coal, South- German bituminous shale, or similar combinations or mixtures may tage for the -manufacture of such sulphonation products. Analogous deposits of coal-like materials which are equally suitable for the process according to this invention, on account of their sulphur content, are found in all parts of the world. Practically it is, of course, preferable to the refinement begin with the' distillates because is thereby simplified.

Example I As starting material a distilled Italian mineral coal-tar, having the following characteristics, is used: specific gravity of about 0.9 at 15; sulphur content 8.8%; boiling points about 90-250. 100 grams of this oil are pre-reflned with a solution of caustic soda of 39 B., sulphuric acid of 10% H2804 and fullers earth. The sulphur content after the pre-refinement is 10.22%.

The refined oil is nowsulphonated with about and cooling at C. The sulphonation mixture is run into water, and sulpho-acid and oil are then neutralized with ammonia. After separating the oil, the product is evaporated to a water content of 41.24%. grams are obtained of this product which, in this condition, contains 6.84% of amof sulphur. The organic substance is 51.92% including 15.24% of sulphur. It has been calculated that the oil substance which has been sulphonated contains 11.01% of organic sulphur. The productis light brown, transparent and clearly water-soluble.

The reaction products of the oil and sulphuric acid obtained in the end product are true sulphoacids and. not esters because the latter would be split by the strong heating which takes place in the dilution of the sulphonation product with water and in the evaporation of the water from the neutralized product.

Example II As starting material a distilled Italian mineral coal-tar is used having the following characteristics; specific gravity of 0.890 at 0.; sulphur content 7.0%; boiling analysis:

. Per cent 101-200 54.3 200-269 "-95 531 grams of this oil are pre-refined with 35% solution of caustic soda, 85% phosphoric acid and fullers earth. The sulphur content after the pre-refinement is 7.2%. The refined oil is now sulphonated with about 480 cc. of sulphuric acid (pure concentrated) under stirring and cooling at about -'5 C., and sulpho-acid and oil are then neutralized with ammonia. After separating the oil, the product is then evaporated to a water content of 42%. 69 grams of this product are obtained. In this condition it contains 11% of ammonium sulphate and 10.62% of sulphur. The organic substance therein is 47%, including 16.92% of sulphur. It has been calculated that be'used with equal advan-' dialysis or by 4 H2804 under stirring of sulphuric acid ring at a temperature 01 about -8 the oil substance which has been sulphonated contains 10.38% of organic sulphur. The product is light-brown, transparent and clearly water:-

, soluble.

Example III As starting material a distilled Mid-German oil is used having the folbrown coal-gas-light speciflc gravity of 0.850

lowing characteristics at 15C.; sulphur content 6.0%; boiling analysis:

. Per cent 80 to 100 2.5 100 to 150 150 to 200 92 500 grams of this oil are pro-refined with solution of caustic, potash and 50% sulphuric acid. The sulphur content of the oil after this pre-refinement still is 5.6%. The refined oil is now sulphonated with about cc. sulphuric acid (pure concentrated) under stirring and cooling at about 0 C. The sulphonation mixture is run into water and neutralized with ammonia. After removal of the unafiected partoi the oil, having become separated by the dilution with water, the product is evaporated to a water content of 30%. 50 grams of this product are obtained. It contains in this condition 8.67% of ammonium sulphate and 10.90% of sulphur. It has been calculated that the sulphonated oil substance contains 8.69% of organic sulphur. The product is light-brown, transparent and soluble.

. Example IV r cent to 1.8 100 to 300- I 61.0 200 to 300 94.1

524 grams of this oil are pre-reflned with waterfree aluminum chloride, 35% solution 01 caustic soda and fullers earth. The sulphur content of the oil after this pre-refinement is still 11%.. The refined- 425 cc. sulphuric acid (pure concentrated) understirring and cooling at about 5 C. The sulphonation mixture is'run into water and sulpho-acid and oil are neutralized with ammonia. of the unaflected part of the oil, having become separated by the dilution with water, the product is evaporated to a water content of 30.5%. grams of this product are obtained. It conta ns in this condition 4.77% of ammonium sulphate and 14.80% of sulphur. The organic substance therein is 64.73%, including 21.07% of sulphur. It has been calculated that the sulphonated oil substance contains 17.53% of organic sulphur. The product is lightbrown, transparent and clearly water-soluble.

g'zample V Per cent to 200; 5a 200 to 287 -L 96.5

are sulphonated with 16 liters 7.15 kg. of thisoil (technical 66 135.) under stiracid and oil clearly wateroil is now sulphonated with about which have their will not impart their oils. naturally rich C. 'lhe sulphonation mixture is run into water and minimaare neutralized with ammonia. A1- ter removal of the unaii'ected part. having become separated by the dilution with water, the evaporated to ,a" water content oi 1.84 kg. or this product are obtained. It contains-in this condition 7.33% of ammonium sulphate and 14.87% of sulphur. The organic substance therein is 68.42%, including 19.13% oi sulphur. The sulphonated oil substance contains 15.04% of organic sulphur. The product is light-brown, transparent and clearly water-soluble.

463 grams of the oil, separated by the dilution of the sulphonation mixture with water, having a specific gravity of 0.926 at 15 C., are diluted with an equal volume of petroleum and with 500 cc. of sulphuric acid (16 weight per cent of 66 Be. technical acid+84 weight per cent of technical fuming acid with 18% of $03) under stirring at a temperatureoi about -15? C. e sulphonation mixture is run into water and sulpho-acid and oil are neutralized with'ammonia. After removal of the unaffected part of the oil, having i:

become separated by the dilution with water, the product is evamrated to a water content of 50%. obtained which,

sulphate and 10.60% oi sulphur. It has been calculated that the sulphonated oil substance contains about 12.8% of organic sulphur. The

product is light-brown, transparent and ciearly water-soluble. Obviously, the various steps of the process may be modified considerably with respect to the order and the number of steps and the speoifio materials used in the several methods exemplliyin'g the pre-treatment and sulphonation steps, without'departing from the spirit of the invention substantially as described and claimed, and it is understood that I do not desire to iimit myself to the specific embodiments shown in the foregoing examples, wherein numerous equivalent materials may be employed as noted.

I claim:

1. Sulphonated sulphur-bearing mineral oils original sulphur content substantially unimpaired, being'of a light yellowbrown color and clearly water-soluble.

2. Sulphonated sulphur-bearing mineral oils which have their original sulphur content substantially unimpaired, being of a light yellowbrown color and clearly water-soluble, and which color to other substances when mixed therewith.

'3. Preparations comprising essentially aqueous solutions of sulphonation products of mineral in organically combined sulphur compounds, having their native sulphur content substantially unimpaired, being substantially neutral in reaction, transparent. of a light eral oil distlllates, naturally rich in organically combined sulphurcompounds, having their native organic sulphur content substantially unimpaired, being transparent, of a light yellowbrown color, clearly water-soluble, and substantially free from objectionable staining-color and odor.

6. An improved sulphur-rich sulphonic compound, comprising essentially the sulphonic reaction product of a sulphonating agent and a sulphur-rich distillate obtained from naturally sulphur-rich bituminous material, said distillate l being. substantially free from resinifiable and objectionable staining-color producing substances. 7

7. The physical and chemical reaction product resulting from the reaction between a sulphonating agent and a mineral-oil distillate, free from resinifiable and color-produc ng substancea-such reaction product containing substantially unimpaired all of the organically combined sulphur compounds of the original native sulphur present in the distillate and the sulphur introduced by the sulphonating agent, and being substantially of a clear, light brownish color, water-soluble, and free from objectionable odor and stainingcolor. I

8. A neutralized physical and chemical reaction product resulting from the reactionbetween a sulphonating agent and a mineral-oil distillate, free from resiniflable and colon-producing substances, such reaction product containing substantially unimpaired all of. the organically combined sulphur compounds of the original native sulphur present in the distillate and the sulphur introduced by the sulphonating agent, and being substantially of a clear, light brownish color, water-soluble, andv free from objectionable odor and staining-color.

- ERICH ARNOLD WERNICKE. 

